Abstract:

Adhesion of perfume esters to surfaces, such as the surfaces of textiles,
of hard objects, or of the human body, was able to be improved. Said
object is achieved substantially by using particular enzymes leading to
improved fixing of the perfume ester on hard and/or soft surfaces.

Claims:

1. Process for fixing perfume esters to a hard or soft surface
comprising:treating a surface at a temperature of about 95.degree. C. or
less for a time of about 1 to about 300 minutes with an aqueous treatment
liquor comprising one or more perfume esters and one or more hydrolases.

2. Process according to claim 1 wherein the one or more hydrolases is at
least glycosidase and/or protease.

3. Process according to claim 2 wherein the one or more hydrolases is at
least glycosidase and the glycosidase is at least hemicellulase and/or
starch-degrading enzymes.

4. Process according to claim 3 wherein the hemicellulase is mannanase.

5. Process according to claim 3 wherein the starch-degrading enzyme is
amylase.

6. Process according to claim 2 wherein the one or more hydrolases is at
least protease and the protease is at least subtilases.

7. Process according to claim 6 wherein the subtilases is subtilisins.

8. Process according to claim 1 wherein the treatment time is from about 2
to about 120 minutes.

9. Process according to claim 1 wherein the temperature of the aqueous
treatment liquor is from about 15.degree. C. to about 90.degree. C.

10. Process according to claim 1 wherein the concentration of the
hydrolase in the aqueous treatment liquor is from about 0.0001 mg/l to
about 0.25 g/l.

11. Process according to claim 1 wherein the concentration of perfume
ester in the aqueous treatment liquor is from about 0.0001 mg/l to about
0.25 g/l.

[0002]The present invention relates to a process for fixing perfume esters
onto hard and/or soft surfaces. The invention further relates to a method
for fixing perfume esters to hard and/or soft surfaces when washing or
cleaning using hydrolases (in particular hemicellulase, protease and/or
amylase). Moreover, the invention relates to a method for
prolonging/enhancing the fragrance effect of the perfume ester in perfume
ester-containing washing or cleaning agents with the use of hydrolases
(in particular hemicellulase, protease and/or amylase).

[0003]When washing textiles or cleaning hard surfaces such as bathroom
tiles, one expects not only visually immaculate cleanliness, but also the
absence of any unpleasant odors on the cleaned textiles or hard surfaces.
Perfume fragrances originating from the cleaning agent, washing agent or
laundry conditioner that provide a pleasant aroma are perceived as
particularly agreeable and enhance the impression of cleanliness. For
example, when hand-washing textiles, normally in a washbasin, many
consumers perceive the remaining aroma in the basin and on the hands as
agreeable. Consumers want laundered washing to have a fragrance that is
not only on the product itself and still noticeable after the wash, but
especially is also still clearly perceptible on the treated object over
several days, ideally even weeks. However, the amount of perfume absorbed
from the wash or rinse step out of the aqueous solution onto the textiles
or other surface is frequently too little to also ensure a perceptible
fragrance impression over a longer time. As perfumes are a particularly
high cost component of washing and cleaning agents, it is preferred to
use them only in low quantities. Loss of these ingredients (for example
in a washing machine) is equally unsatisfactory for the manufacturer and
the consumer of such agents.

[0004]Surprisingly, it has now been found that by adding certain enzymes,
namely hydrolases, preferably chosen from a) glycosidases such as a1)
hemicellulases, particularly preferably mannanase and/or, a2)
starch-degrading enzymes, particularly preferably amylase and/or, b)
proteases such as subtilases, especially subtilisins, the adhesion of
perfume esters on a variety surfaces such as textiles, hard objects or on
the skin can be improved if these enzymes are used together with perfume
ester(s) when washing or cleaning the surfaces.

[0005]Based on this background, in one embodiment the present invention
provides a process for fixing or adhering perfume esters to hard and/or
soft surfaces, wherein the surface is treated at a temperature below
95° C. for a period of 1 minute to 300 minutes with an aqueous
treatment liquor comprising perfume ester(s) and hydrolases(s). In a
preferred embodiment of the invention, the hydrolase is chosen from
[0006]a) glycosidases, preferably [0007]a1) hemicellulases, particularly
preferably mannanase and/or, [0008]a2) starch-degrading enzymes,
particularly preferably amylase and/or, [0009]b) proteases, preferably
subtilases, especially subtilisins.Mannanase, protease and/or amylase are
particularly preferably used.

[0010]It has been found that this process for treating hard and/or soft
surfaces with an aqueous treatment liquor comprising perfume ester(s) and
the previously cited enzyme(s) results in a "fixing" (i.e., an improved
adhesion) of the perfume ester onto the treated hard and/or soft
surfaces, resulting in a prolonged and enhanced fragrance effect of the
perfume ester(s), especially on the dry surface. The fragrance linked to
the perfume ester is not only perceptible on the product itself and
immediately after washing, but remains clearly perceptible for a
plurality of days, ideally even weeks after the washing or cleaning step
or treatment step occurred. In other words, a better perceptible
fragrance impression can be ensured on the treated surfaces for a longer
time.

[0011]In this regard, inventively treated surfaces, especially textiles,
after treatment and then preferably dried, smelled particularly
intensively in an olfactory evaluation on the dried object seven (7) days
after the treatment. Here, the improved fragrance impression is due to
the perfume ester, whose fragrance emanates from the inventively treated
surface, as attested by trained olfactory experts in an olfactory
evaluation on the dried object seven (7) days after treatment.

[0012]Further, perfume compositions (e.g. perfume oils, meaning fragrant
mixtures of at least two or more perfumes) benefit from the presence of
the perfume ester so that the fragrance effect of other perfumes is
prolonged, thereby prolonging the overall fragrance effect of the perfume
ester-containing perfume composition. The prolonged overall fragrance
effect or fragrance boost, especially on the dried object, is due to the
existence of perfume ester in the perfume composition. Perfume esters are
present in the total perfume composition in amounts of at least 1 wt. %,
preferably at least 2 wt. % and especially at least 10 wt. %, based on
total amount of the perfumes. This limit can also be higher, for example,
at least 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 40 wt. % or 50 wt. %,
wt. % based on total amount of the comprised perfumes. This limit can
still be even higher, for example, at least 60 wt. %, 70 wt. %, 80 wt. %
or 90 wt. %, wt. % being based on total amount of perfumes.

[0013]Soft surfaces in the context of this invention include skin, as well
as hair and especially textiles of various compositions (e.g., cotton,
wool, silk, polyester, polyamide, viscose and blended fabrics of any
type). Hard surfaces include typical hard surfaces such as glass, metal,
porcelain, ceramic and stoneware, especially in the household sector and
sanitary sector (e.g., in the form of dishes, pots, plates, pans, floors,
windows, tiles, flagstones etc.).

[0017]Enzymes (hydrolases, such as especially mannanase, protease and/or
amylase) used according to the invention can also be absorbed on carrier
materials and/or embedded in encapsulants. This corresponds to a
preferred embodiment of the invention. This allows them to be protected
even better when needed against a premature inactivation.

[0019]It is known to add proteases as protein-cleaving enzymes in washing
and cleaning agents for removing corresponding protein-containing stains.
In contrast, use of proteases (preferably subtilases, especially
subtilisins) in washing or cleaning agents or cosmetics for the purpose
of improving the fragrance impression of perfume esters according to the
present invention was previously unknown.

[0020]In addition to proteases obtained from various Bacillus species or
genetically modified proteases such as Alcalase®, Esperase®,
Savinase®, Durazym® or Everlase®, useful proteases include
those from Bacillus lentus (BLAP) that are stable and active under
alkaline conditions. These can be produced in Bacillus lentus (DSM 5483)
as described in international patent application WO 91/02792, or also by
fermentation of Bacillus licheniformis that has been transformed with an
expression plasmid carrying the gene for BLAP under the control of the
promoter from Bacillus licheniformis ATCC 53926. The composition as well
as the spatial structure of BLAP is known (D. W. Godette et al., J. Mol.
Biol. Vol. 228, pp. 580-595 (1992)). This protease is characterized by
the sequence of 269 amino acids described in the cited reference, a
calculated molecular weight of 26,823 Dalton and a theoretical
isoelectric point of 9.3. Variants obtained by mutation of this Bacillus
lentus DSM 5483 protease are described in U.S. Pat. No. 5,340,735. Among
these, protease enzymes are preferred that cause a particularly low
material damage or decomposition of the fiber strands of textiles made of
proteinogenic fibers, for example, fabrics of natural silk or wool,
without loss of cleaning power, particularly for repeated washings.

[0021]Particularly useable proteases include, beside naturally occurring
proteases from Bacillus lentus, also genetically modified proteases of
the abovementioned BLAP type, in which the amino acid leucin (L in the
conventional one letter code) present in the wild type protease in
position 211 (BLAP numerotation), is exchanged for aspartic acid (D) or
glutamic acid (E) (L211 D or L211 E). They can be manufactured as
described in International Patent Application Publication No. WO
95/23221.

[0022]Additionally, further modifications to the original Bacillus lentus
protease can be undertaken such as at least one of the amino acid
exchanges S3T, V4I, R99G, R99A, R99S, Al 88P, V193M and/or V199I. Use of
a variant is particularly preferred wherein at least one of the amino
acid exchanges S3T, V4I, A188P, V193M, V199I and/or L211 D was
undertaken. In the protease nomenclature described above for the exchange
of individual amino acids, it should be noted that numeration of the
amino acid positions in the numbering of the alkaline proteases from
Bacillus lentus (BLAP) differs from numbering of the subtilisin BPN'.

[0023]It should be made clear here that with the term "useful agent",
reference is made to the inventive process and inventive use described
further below, in the sense that the inventively employable or useful
agent (e.g., a washing agent comprising perfume ester and hydrolase such
as mannanase) is used in the inventive process, for example, the agent in
question is used to prepare the aqueous treatment liquor required for the
process.

[0024]Preferably, starch-degrading enzymes, especially amylases, can be
inventively added in order to anchor perfume esters on hard and/or soft
surfaces. Amylases normally play the role of facilitating the removal of
starch-containing soils by the catalytic hydrolysis of the starch
polysaccharide. In the scope of the invention, one can preferably use
amylases of the α-type from Bacillus licheniformis (sold, for
example, by Novozymes Co. under the trade name Termamyl®), as well as
genetically modified amylases (i.e., those with genetically changed amino
acid sequences with respect to the naturally occurring amylases such as
those known from international patent applications WO 94/18314 or WO
95/21247). Examples of further useable amylases according to the
invention include the α-amylase from Bacillus licheniformis, the
α-amylases from B. amyloliquefaciens, from B. stearothermophilus,
from Aspergillus niger and A. oryzae, as well as their improved further
developments for use in laundry detergents and cleaning agents. Moreover,
for these purposes, attention should be drawn to the α-amylase from
Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin-glucanotransferase
(CGTase) from B. agaradherens (DSM 9948). Use of amylases in washing or
cleaning agents or cosmetics for improving the fragrance impression of
perfume esters, as has been surprisingly discovered by us, appears to be
previously unknown.

[0025]In addition, enzymes which are summarized by the term hemicellulases
can be inventively added. These include mannanases, xanthanlyases,
pectinlyases (=pectinases), pectinesterases, pectatlyases, xyloglucanases
(=xylanases), pullulanases and β-glucanases. In this regard,
suitable enzymes are available under the names Gamanase® and Pektinex
AR® from the Novozymes Company, under the names Rohapec® B1 L
from AB Enzymes and under the names Pyrolase® from Diversa Corp., San
Diego, Calif., USA. β-Glucanase, extracted from B. Subtilis, is
available under the name Cereflo® from the Novozymes Company.
Hemicellulases that are particularly preferred include mannanases (e.g.,
those marketed for example under the tradenames Mannaway® from the
Novozymes Company or Purabrite® from the Genencor Company). Mannanase
can be employed in washing or cleaning agents normally to remove
mannan-containing residues in textile washing. Use of mannanases in
washing or cleaning agents or cosmetics for the purpose of improving the
fragrance impression of perfume esters as has been surprisingly
discovered by us, appears to be previously unknown.

[0026]According to a preferred embodiment of the process according to the
invention, the treatment time of the surface with the aqueous treatment
liquor is the range of about 2 to about 120 minutes, especially from
about 10 minutes to about 80 minutes. If the temperature of the aqueous
treatment liquor is in the range of about 15° C. to about
90° C., especially from about 20° C. to about 60°
C., then this is also a preferred embodiment of the process according to
the invention. In this regard it is particularly advantageous if the
temperature of the aqueous treatment liquor is in the range of about
20° C. to about 60° C. during the length of treatment time.
By doing so, particularly good fragrance results are achieved, especially
for dry objects. It should be understood that the term "dry object"
refers to surfaces such as textiles that were first subjected to a
process according to the invention and consequently came into contact
with an inventive aqueous treatment liquor (L e., were wet and afterwards
were left to dry, for example in ambient air, or were subjected to a
drying step, for example in a tumble drier).

[0027]According to a preferred embodiment of the process according to the
invention, the concentration of the inventively employable hydrolase in
the aqueous treatment liquor is in the range of about 0.0001 mg/l to
about 0.25 g/l, especially from about 0.01 mg/l to about 15 mg/l.
According to a preferred embodiment of the process according to the
invention, the concentration of the inventively employable perfume ester
in the aqueous treatment liquor is in the range of about 0.0001 g/l to
about 0.25 g/l, especially from about 0.001 g/l to about 0.05 g/l. A
likewise preferred embodiment of the process according to the invention
is when the treatment liquor contains anionic and/or non-ionic
surfactant. Surprisingly, the effect of the inventive fixing of perfume
esters could be confirmed, particularly also in the presence of greater
amounts of anionic and/or non-ionic surfactant in an inventively
employable agent (e.g., in amounts > about 5 wt. %, > about 10 wt.
% or even > about 15 wt. %, based on the total agent).

[0028]Another subject matter of the invention concerns a method for fixing
perfume esters on hard and/or soft surfaces when washing or cleaning the
hard and/or soft surfaces with perfume ester-containing treatment agents
with the use of hydrolases (preferably selected from a) glycosidases,
preferably a1) hemicellulases, particularly preferably mannanase and/or,
a2) starch-degrading enzymes, particularly preferably amylase and/or, b)
proteases, preferably subtilases, especially subtilisins). The fixing,
meaning an improved adhesion, yields, as described above, a
prolonged/enhanced fragrance effect of the perfume ester on the treated
surface, especially on the dry object, while promoting the fragrance
effect of other perfumes if a perfume ester-containing perfume
composition is used, again especially on the dry object, which can be
confirmed by odor assessment of the treated object, preferably by
perfumers, especially 7 days after drying. The just mentioned inventive
method for fixing perfume esters on surfaces is particularly
advantageous, especially when washing textiles, preferably in an
automatic washing machine. Another advantage is that this inventive
fixing then also even involves a prolonged/enhanced fragrance effect of
the perfume ester on the treated surface if the laundered textile washing
is subsequently subjected to a textile drying step in an automatic
textile dryer, in particular in a vented or condensing dryer. This is a
particular advantage because it is often the case that the fragrance of
the textile to be dried is lost to a very considerable degree in the
drying step in an automatic textile dryer.

[0030]Another subject matter of the present invention concerns a method
for prolonging/enhancing the fragrance effect of the perfume ester in
perfume ester-containing liquid or solid washing or cleaning agents,
after the washing or cleaning application on a hard and/or soft surface
to be treated, especially relating to the dry object, with the use of
hydrolases (preferably selected from a) glycosidases, preferably a1)
hemicellulases, particularly preferably mannanase and/or, a2)
starch-degrading enzymes, particularly preferably amylase and/or, b)
proteases, preferably subtilases, especially subtilisins). The described
prolonging/enhancing of the fragrance effect of the perfume ester is the
result of its improved fixing onto the treated surface. The volatility of
the perfume ester is slowed down by the improved fixing. Improved fixing
does not mean that the deposition of the perfume ester onto the surfaces
is improved, rather that the deposited perfume adheres better.

[0031]It is particularly preferred if the washing or cleaning agent in
question comprises the hydrolase (preferably selected from a)
glycosidases, preferably a1) hemicellulases, particularly preferably
mannanase and/or, a2) starch-degrading enzymes, particularly preferably
amylase and/or, b) proteases, preferably subtilases, especially
subtilisins) in amounts of about 0.0000001 to about 5 wt. %, preferably
about 0.000001 to about 4 wt. %, advantageously about 0.00001 to about 3
wt. %, more advantageously about 0.0001 to about 2 wt. %, further
advantageously 0.001 to about 1 wt. %, even more advantageously 0.01 to
about 0.5 wt. %, particularly about 0.05 to about 0.1 wt. %, wt. % based
on the total agent. The cited upper and lower limits can be varied, such
that the hydrolase can be comprised in the washing or cleaning agent in
question in amounts of about 0.00001 to about 0.1 wt. %, e.g. in amounts
of about 0.00001 to about 0.072 wt. % based on total agent.

[0033]As already clarified, the process according to the invention can be
carried out with a typical agent that includes the perfume ester and the
hydrolase. The same is true for the method according to the invention.
Such a typical agent that comprises the perfume ester and hydrolase can
be in particular a textile washing agent or textile-care product, which
can be in particulate or liquid form, a cleaning agent in a suitable form
for hard surfaces, for example a tile cleaner, a bath cleaner or sanitary
cleaner, or a cleaning agent for the human body, for example a hair
shampoo, a cleaning lotion, a shower gel or a piece of soap. In
particular, the inventive teaching can also be employed in the field of
personal hygiene.

[0034]In addition, inventively employable agents include powdered solids,
in post-compressed particulate form, in molded form (especially tablet
form) as homogeneous solutions or suspensions, and can contain all the
usual ingredients that are suitable for the use of the corresponding
agents.

[0036]The inventively employable agents, particularly washing or cleaning
agents, can preferably comprise surfactants such as anionic surfactants,
non-ionic surfactants and their mixtures, but also cationic surfactants.
Suitable non-ionic surfactants include ethoxylation and/or propoxylation
products of alkyl glycosides and/or linear or branched alcohols, each
with 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4
to 10 alkyl ether groups. Moreover, corresponding ethoxylation and/or
propoxylation products of N-alkylamines, vicinal diols, fatty acid esters
and fatty acid amides, which in regard to the alkyl moiety correspond to
the cited long chain alcohol derivatives, as well as alkyl phenols with 5
to 12 carbon atoms in the alkyl group can be used.

[0037]Suitable anionic surfactants include soaps and such that comprise
sulfate or sulfonate groups, preferably with alkali metal ions as the
cations. Useful soaps include alkali metal salts of saturated or
unsaturated fatty acids with 12 to 18 carbon atoms. These types of fatty
acids can also be used in a not completely neutralized form. Useful
sulfate surfactants include the salts of sulfuric acid half esters of
fatty alcohols with 12 to 18 carbon atoms and the sulfation products of
the mentioned non-ionic surfactants with a low degree of ethoxylation.
Useful sulfonate surfactants include linear alkylbenzene sulfonates with
9 to 14 carbon atoms in the alkyl moiety, alkyl sulfonates with 12 to 18
carbon atoms, as well as olefin sulfonates with 12 to 18 carbon atoms,
which result from the reaction of corresponding monoolefins with sulfur
trioxide, as well as α-sulfofatty acid esters that result from the
sulfonation of fatty acid methyl or ethyl esters.

[0038]Cationic surfactants are preferably selected from the esterquats
and/or the quaternary ammonium compounds (QUATS) according to the general
formula (RI)(RII)(RIII)(RIV)N+X.sup.-, in which
RI to RIV may be the same or different C1-22 alkyl groups,
C7-28 arylalkyl groups or heterocyclic groups, wherein two or, in
the case of an aromatic bonding such as in pyridine, even three groups
together with the nitrogen atom form the heterocycle, for example, a
pyridinium or imidazolinium compound, and X.sup.- represents halide ions,
sulfate ions, hydroxide ions or similar anions. QUATS can be obtained by
reacting tertiary amines with alkylating agents such as methyl chloride,
benzyl chloride, dimethyl sulfate, dodecyl bromide, as well as ethylene
oxide. The alkylation of tertiary amines having one long alkyl chain and
two methyl groups is particularly easy. The quaternization of tertiary
amines containing two long chains and one methyl group can also be
carried out under mild conditions using methyl chloride. Amines
containing three long alkyl chains or hydroxy-substituted alkyl chains
lack reactivity and are quaternized with dimethyl sulfate, for example.
Suitable QUATS include benzalkonium chloride
(N-alkyl-N,N-dimethylbenzylammonium chloride, Benzalkon B
(m,p-dichlorobenzyl dimethyl-C12-alkylammonium chloride, Benzoxonium
chloride (benzyldodecyl-bis-(2-hydroxyethyl)ammonium chloride),
Cetrimonium bromide (N-hexadecyl-N,N-trimethyl ammonium bromide,
Benzetonium chloride
(N,N-di-methyl-N-[2-[2-[p-(1,1,3,3-tetramethylbutyl)-phenoxy]ethoxy]-ethy-
l]-benzylammonium chloride, dialkyldimethylammonium chlorides, such as
di-n-decyldimethylammonium chloride, didecyldimethylammonium bromide,
dioctyldimethylammonium chloride, 1-cetylpyridinium chloride and
thiazoline iodide and mixtures thereof. Preferred QUATS are the
benzalkonium chlorides containing C8-C22 alkyl groups, more
particularly C12-14 alkylbenzyldimethylammonium chloride.

[0039]Ester quats include compounds of the general Formula I

##STR00001##

wherein R5 is an alkyl or alkenyl group with 12 to 22 carbon atoms
and 0, 1, 2 or 3 double bonds; R6 and R7 are each independently
H, OH or O(CO)R5; s, t and u are each independently 1, 2 or 3; and
X.sup.- is an anion, particularly halide, methosulfate, methophosphate or
phosphate as well as mixtures thereof. Preferred compounds comprise a
group O(CO)R5 for R6 and an alkyl group with 16 to 18 carbon
atoms for R5. Particularly preferred are compounds in which R7
stands for OH. Examples of compounds according to Formula (V) include
methyl-N-(2-hydroxyethyl)-N,N-di(tallowacyloxyethyl)ammonium
methosulfate, bis(palmitoyl)ethylhydroxyethylmethylammonium methosulfate
or methyl-N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)ammonium methosulfate.
When quaternized compounds of Formula (V) are used that have unsaturated
groups, the acyl groups are preferred, whose corresponding fatty acids
have an iodine number between 5 and 80, preferably between 10 and 60 and
particularly between 15 and 45 and/or which have a cis/trans isomer ratio
(in mol %) of greater than 30:70, preferably greater than 50:50 and in
particular greater than 70:30. Commercial examples are the
methylhydroxyalkyldialcoyloxyalkylammonium methosulfates marketed by the
Stepan company under the trade name Stepantex® or known products from
Cognis Deutschland GmbH with the trade name Dehyquart® or the known
products manufactured by Goldschmidt-Witco under the name Rewoquat®.

[0040]Surfactants can be included in the inventively employable agents, in
particular in washing or cleaning agents, in amounts of about 5 wt. % to
about 50 wt. %, especially from about 8 wt. % to 3 about 0 wt. %.
Preferably up to about 30 wt. %, especially about 5 wt. % to about 15 wt.
% of surfactants, among which at least a part is preferably cationic
surfactants, are present in inventively employable laundry conditioners.

[0042]The relative molecular weight of homopolymers of unsaturated
carboxylic acids is generally from about 5000 to about 200,000 m, and for
copolymers is from about 2000 to about 200,000, preferably from about
50,000 to about 120,000, each based on the free acid. A particularly
preferred acrylic acid-maleic acid copolymer has a relative molecular
weight of about 50,000 to about 100,000.

[0043]Suitable, yet less preferred compounds of this class include
copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as
vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in
which the content of the acid is at least 50 wt. %.

[0044]Terpolymers, which comprise two unsaturated acids and/or their salts
as monomers as well as vinyl alcohol and/or a vinyl alcohol derivative or
a carbohydrate as the third monomer, can also be used as the
water-soluble organic builders. The first acid monomer or its salt is
derived from a monoethylenically unsaturated C3-C8 carboxylic
acid and preferably from a C3-C4 monocarboxylic acid,
particularly from (meth)acrylic acid. The second acid monomer or its salt
can be a derivative of a C4-C8 dicarboxylic acid, maleic acid
being particularly preferred. In this case the third monomer unit is
formed from vinyl alcohol and/or preferably an esterified vinyl alcohol.
In particular, vinyl alcohol derivatives are preferred which represent an
ester of short chain carboxylic acids, for example C1-C4
carboxylic acids, with vinyl alcohol. Preferred polymers comprise from
about 60 wt. % to about 95 wt. %, particularly about 70 wt. % to about 90
wt. % (meth)acrylic acid or (meth)acrylate, particularly preferably
acrylic acid or acrylate, and maleic acid or maleate as well as about 5
wt. % to about 40 wt. %, preferably about 10 wt. % to about 30 wt. %
vinyl alcohol and/or vinyl acetate. Polymers are quite particularly
preferred, in which the weight ratio (meth)acrylic acid or (meth)acrylate
to maleic acid or maleate is from about 1:1 to about 4:1, preferably from
about 2:1 to about 3:1 and particularly about 2:1 to about 2.5:1. Here,
both the quantities and the weight ratios are based on the acids. The
second acid monomer or its salt can also be a derivative of an allyl
sulfonic acid, which is substituted in the 2-position with an alkyl
group, preferably a C1-C4 alkyl group, or an aromatic group
that is preferably derived from benzene or benzene derivatives. Preferred
terpolymers comprise about 40 wt. % to about 60 wt. %, particularly about
45 wt. % to about 55 wt. % (meth)acrylic acid or (meth)acrylate,
particularly preferably acrylic acid or acrylate, about 10 wt. % to about
30 wt. %, preferably about 15 wt. % to about 25 wt. % methallyl sulfonic
acid or methallyl sulfonate and as the third monomer about 15 wt. % to
about 40 wt. %, preferably about 20 wt. % to about 40 wt. % of a
carbohydrate. This carbohydrate can, for example, be a mono, di, oligo or
polysaccharide, mono, di or oligosaccharides being preferred. Saccharose
is particularly preferred. Adding the third monomer presumably creates
intended weak points in the polymer, which are responsible for the good
biological degradation of the polymer. In general, terpolymers possess a
relative molecular weight from about 1000 to about 200,000, preferably
from about 200 to about 50,000 and particularly from about 3000 to about
10,000. Other preferred copolymers are those which preferably contain
acrolein and acrylic acid/acrylic acid salts or vinyl acetate as
monomers.

[0045]Organic builders, especially for the manufacture of liquid agents,
can be added in the form of aqueous solutions, preferably in the form of
about 30 to about 40 weight percent aqueous solutions. In general, all
cited acids are added in the form of their water-soluble salts,
particularly their alkali metal salts. These types of organic builders
can be comprised as desired in amounts of up to about 40 wt. %,
particularly up to about 25 wt. % and preferably from about 1 wt. % to
about 8 wt. % in the inventively employable agents. Amounts close to the
cited upper limit are preferably added in pasty or liquid, particularly
aqueous, inventively employable agents. Inventively employable laundry
conditioners can optionally also be exempt of organic builders.

[0046]Alkali metal silicates and polyphosphates, preferably sodium
triphosphate are especially used as the water-soluble builders for the
inventively employable agents. In particular, crystalline or amorphous
alkali metal aluminosilicates in amounts of up to about 50 wt. %,
preferably not more than about 40 wt. % and in liquid agents not more
than about 1 wt. % to about 5 wt. % are added as the water-insoluble,
water-dispersible inorganic builders. Among these, the detergent-quality
crystalline sodium aluminosilicates, particularly zeolites A, P and
optionally X, are preferred. Amounts close to the cited upper limit are
preferably incorporated in solid, particulate agents. Suitable
aluminosilicates particularly exhibit no particles with a particle size
above about 30 μm and preferably include at least about 80 wt. % of
particles smaller than 10 μm. Their calcium binding capacity,
determined according to the usual methods, generally lies in the range of
about 100 to about 200 mg CaO per gram.

[0047]Suitable substitutes or partial substitutes for the cited
alumosilicate are crystalline alkali metal silicates that can be alone or
present in a mixture with amorphous silicates. The alkali metal silicates
useful as builders in the inventively employable agents preferably have a
molar ratio of alkali metal oxide to SiO2 below about 0.95,
particularly about 1:1.1 to about 1:12 and can be amorphous or
crystalline. Preferred alkali metal silicates include sodium silicates,
particularly amorphous sodium silicates, with a molar ratio
Na2O:SiO2 of about 1:2 to about 1:2.8. Crystalline silicates
that can be present alone or in a mixture with amorphous silicates are
preferably crystalline, layered silicates corresponding to the general
formula Na2SixO2x+1yH2O, wherein x, the so-called
module, is a number from 1.9 to 4 and y is a number from 0 to 20,
preferred values for x being 2, 3 or 4. Preferred crystalline layered
silicates are those in which x assumes the values 2 or 3 in the cited
general formula. In particular, both β- and δ-sodium
disilicates (Na2Si2O5yH2O) are preferred. Practically
anhydrous crystalline alkali metal silicates of the abovementioned
general formula in which x is a number from 1.9 to 2.1 can also be
manufactured from amorphous alkali metal silicates, and can be used in
inventively employable agents. In a further preferred embodiment of the
inventively employable agent, a crystalline sodium layered silicate with
a module of 2 to 3 is added, as can be manufactured from sand and soda.
In a further preferred embodiment of the inventive agent, crystalline
sodium silicates with a module in the range 1.9 to 3.5 can be added. When
alkali metal aluminosilicate, in particular zeolite, is also present as
the additional builder, then the weight ratio aluminosilicate to
silicate, each based on the anhydrous active substances, is preferably
1:10 to 10:1. In agents containing both amorphous and crystalline alkali
metal silicates, the weight ratio of amorphous alkali metal silicate to
crystalline alkali metal silicate is preferably 1:2 to 2:1 and
particularly 1:1 to 2:1.

[0048]Builders can be present in the inventively employable agents, in
particular washing agents, preferably in amounts of up to about 60 wt. %,
especially from about 5 wt. % to about 40 wt. %. Inventively employable
laundry conditioners are preferably exempt from inorganic builders.

[0049]Suitable peroxygen compounds that may be used in the inventively
employable agents particularly include organic peracids or peracid salts
of organic acids such as phthalimide percaproic acid, perbenzoic acid or
salts of diperoxydodecanedioic acid, hydrogen peroxide and inorganic
salts that liberate hydrogen peroxide under the application conditions,
such as perborate, percarbonate and/or persilicate. If solid peroxygen
compounds are used, then they can be used in the form of powders or
pellets, which can also be encapsulated by known methods. Alkali
percarbonate, alkali perborate monohydrate or particularly in liquid
agents hydrogen peroxide in the form of aqueous solutions that comprise
about 3 wt. % to about 10 wt. % hydrogen peroxide are particularly
preferably used. When an inventive washing agent comprises peroxygen
compounds then the latter are present in amounts of preferably up to
about 50 wt. %, especially about 5 wt. % to about 30 wt. %. The addition
of minor quantities of known bleaching agent activators such as
phosphonates, borates or metaborates and metasilicates, as well as
magnesium salts such as magnesium, can be useful.

[0050]Useful bleach activators include compounds which, under
perhydrolysis conditions, yield aliphatic peroxycarboxylic acids having
preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms,
and/or optionally substituted perbenzoic acid. Substances, which carry
O-acyl and/or N-acyl groups of said number of carbon atoms and/or
optionally substituted benzoyl groups, are suitable. Polyacylated
alkylenediamines are preferred, especially tetraacetylethylenediamine
(TAED), as well as acylated phenol sulfonates, in particular n-nonanoyl-
or isononanoyloxybenzene sulfonate (n- or iso-NOBS). Combinations of
conventional bleach activators may also be used. These types of bleach
activators can be included in usual quantity range of about 1 to about 10
wt. %, particularly about 2 wt. % to about 8 wt. %, based on total
employable agent.

[0051]In addition to or instead of the above-listed conventional bleach
activators, inventively employable agents can also include sulfonimines
and/or bleach boosting transition metal salts or transition metal
complexes as so-called bleach catalysts. The possible transition metal
compounds include, in particular, salen complexes of manganese, iron,
cobalt, ruthenium or molybdenum and their analogous N-compounds, the
carbonyl complexes of manganese, iron, cobalt, ruthenium or molybdenum,
the nitrogen-containing tripod ligand complexes of manganese, iron,
cobalt, ruthenium, molybdenum, titanium, vanadium and copper, and the
ammine complexes of cobalt, iron, copper and ruthenium. Combinations of
bleach activators and transition metal bleach catalysts can likewise be
employed. Bleach boosting transition metal complexes, in particular with
the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, can be added in
usual amounts, preferably in an amount of up to 1 wt. %, particularly
from 0.0025 wt. % to 0.25 wt. % and particularly preferably from 0.01 to
0.1 wt. %, each based on the total agent.

[0052]Additionally employable enzymes in the inventively employable agents
can include those from the classes of the cutinases, pullulanases,
hemicellulases, cellulases, lipases, oxidases and peroxidases as well as
mixtures thereof. Enzymatic active materials obtained from bacterial
sources or fungi such as Bacillus subtilis, Bacillus licheniformis,
Streptomyceus griseus, Humicola lanuginosa, Humicola insolens,
Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly
suitable. These optionally employable enzymes can be adsorbed on carriers
and/or embedded in encapsulants in order to protect them against
premature inactivation.

[0054]Suitable foam inhibitors include organopolysiloxanes and mixtures
thereof with microfine, optionally silanized silica and also paraffin
waxes and mixtures thereof with silanized silica or bis-fatty acid
ethylenediamides. Mixtures of different foam inhibitors, for example
mixtures of silicones, paraffins or waxes, are also used with advantage.
Preferably, the foam inhibitors, especially silicone-containing and/or
paraffin-containing foam inhibitors, are loaded onto a granular,
water-soluble or dispersible carrier material. Especially in this case,
mixtures of paraffins and bis-stearylethylenediamides are preferred.

[0055]In addition, the inventively employable agents can also comprise
components that positively influence oil and fat removal from textiles
during the wash, so-called soil release active substances. This effect is
particularly noticeable when a textile is soiled and had been previously
already washed several times with a washing agent that comprised this
oil- or fat-removing component. The preferred oil and fat removing
components include, for example, non-ionic cellulose ethers such as
methyl cellulose and methyl hydroxypropyl cellulose with a content of
methoxy groups of about 15 to about 30 wt. % and hydroxypropoxy groups of
about 1 to about 15 wt. %, each based on the non-ionic cellulose ether,
as well as polymers of phthalic acid and/or terephthalic acid or their
derivatives with monomeric and/or polymeric diols known from the prior
art, particularly polymers of ethylene terephthalates and/or polyethylene
glycol terephthalates or anionically and/or non-ionically modified
derivatives thereof.

[0056]The inventively employable agents can also comprise color transfer
inhibitors, preferably in amounts of about 0.1 wt. % to about 2 wt. %,
especially about 0.1 to about 1 wt. % which in a preferred development of
the invention are polymers of vinyl pyrrolidone, vinylimidazole,
vinylpyridine N-oxide or copolymers of these. Both polyvinyl pyrrolidones
with molecular weights of about 15,000 to about 50,000, as well as
polyvinyl pyrrolidones with molecular weights over about 1,000,000, in
particular from about 1,500,000 to about 4,000,000,
N-vinylimidazole/N-vinyl pyrrolidone copolymers, polyvinyloxazolidones,
copolymers based on vinyl monomers and carboxylic acid amides,
pyrrolidone group-containing polyesters and polyamides, grafted polyamido
amines and polyethylene imines, polymers with amide groups from secondary
amines, polyamine N-oxide polymers, polyvinyl alcohols and copolymers
based on acrylamido alkenyl sulfonic acids can be employed. However,
enzymatic systems which include a peroxidase and hydrogen peroxide or a
substance that releases hydrogen peroxide in water can also be added. The
addition of a mediator compound for the peroxidase, for example, an
acetosyringone, a phenol derivative or a phenothiazine or phenoxazine is
preferred in this case, wherein in addition, the above-mentioned
polymeric color transfer inhibitor active substances can also be used. In
agents according to the invention, polyvinyl pyrrolidone with an average
molecular weight of about 10,000 to about 60,000, particularly about
25,000 to about 50,000, is preferably added. Preferred copolymers are
those of vinyl pyrrolidone and vinylimidazole with a molar ratio of about
5:1 to about 1:1, with an average molecular weight of about 5000 to about
50,000, particularly about 10,000 to about 20,000.

[0057]Graying inhibitors have the task of ensuring that the dirt removed
from the textile fibers is held suspended in the wash liquid.
Water-soluble colloids of mostly organic nature are suitable for this,
for example starch, glue, gelatines, salts of ether carboxylic acids or
ether sulfonic acids of starches or celluloses, or salts of acidic
sulfuric acid esters of celluloses or starches. Water-soluble, acid
group-containing polyamides are also suitable for this purpose. Moreover,
aldehyde starches, for example, can be used instead of the abovementioned
starch derivatives. Preference, however, is given to the use of cellulose
ethers such as carboxymethyl cellulose (Na salt), methyl cellulose,
hydroxyalkyl cellulose, and mixed ethers, such as methyl hydroxyethyl
cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose
and mixtures thereof, which can be added, for example, in amounts of
about 0.1 to about 5 wt. %, based on the agent.

[0058]Organic solvents that can be employed in the inventive agents,
particularly when the agents are in liquid or paste form, include
alcohols with 1 to 4 carbon atoms, particularly methanol, ethanol,
isopropanol and tert.-butanol, diols with 2 to 4 carbon atoms,
particularly ethylene glycol and propylene glycol, their mixtures and the
ethers derived from the cited classes of compounds. These types of
water-miscible solvents can be comprised in the inventively employable
agents, such as in particular washing or cleaning agents, preferably in
amounts of not more than about 30 wt. %, especially from about 6 wt. % to
about 20 wt. %.

[0059]To adjust a pH resulting from mixing the usual components to a
desired level, the inventive agents can comprise acids that are
compatible with the system and the environment, particularly citric acid,
acetic acid, tartaric acid, malic acid, glycolic acid, succinic acid,
glutaric acid and/or adipic acid, and also mineral acids, particularly
sulfuric acid or bases, particularly ammonium hydroxide or alkali metal
hydroxides. These types of pH adjustors can be comprised in the
inventively employable agents at not more than about 20 wt. %, especially
about 1.2 wt. % to about 17 wt. %.

[0060]The manufacture of solid inventively employable agents is not
difficult and in principle can be made by known methods such as spray
drying or granulation, wherein the peroxygen compound and bleach
catalyst, when comprised, are optionally added later. For manufacturing
inventively employable agents with an increased bulk density,
particularly in the range of 650 g/l to 950 g/l, a preferred process is
one with an extrusion step.

[0061]According to another preferred embodiment, the inventive teaching
can be used in order to significantly decrease the perfume content in
washing, cleaning and body care agents. This enables perfumed products to
be offered even to those particularly sensitive consumers, who, due to
specific intolerances and irritations, can only make limited use or are
absolutely unable to use normally perfumed products. Hand washing agents,
for example may be mentioned in this regard.

[0063]The hand towels were washed three times under the conditions listed
above with inventive washing agent W1 that comprised 0.01 wt. % mannanase
and, after the last wash, were dried in ambient air. In parallel, hand
towels were treated under the same conditions with the comparative
washing agent V1 (i.e., containing no mannanase). The textiles were
presented to 6 trained and experienced perfumers and subjected to a
comparative odor evaluation by them. The fragrance impression was
assessed both for the damp washing as well as for dry washing after 7
days storage on an open shelf.

[0064]While the fragrance impression on damp washing was comparable, the
addition of the inventive agent W1 on the dry washing after 7 days
storage on an open shelf afforded a distinctly more intensive fragrance
than with the addition of V1. This test was repeated under exactly the
same conditions and gave the same result.

[0065]The washing agents X1 and Y1 were then tested against V1 under the
same conditions as described above. X1 differed from V1 only in that it
comprised 0.01 wt. % protease. Z1 differed from V1 only in that it
comprised 0.01 wt. % amylase. The addition of the inventive agent X1 on
the dry washing after 7 days storage on an open shelf afforded a
distinctly more intensive fragrance than with the addition of V1. The
fragrance impression on damp washing was comparable. The addition of the
inventive agent Z1 on the dry washing after 7 days storage on an open
shelf afforded a distinctly more intensive fragrance than with the
addition of V1. The fragrance impression on damp washing was comparable.